Coumarone base



Patented Sept. 28, 1937 PATENT A OFFICE 2,094,331 OOUMARONE BASE JosephRivkin,

Neville Company, a vania Pittsburgh, a... assignor to The corporation ofPennsyl- No Drawing. Application July 9, 1936, Serial No. 89,769

7 Claims.

This invention relates to a modified eoumarone resin made up withChina-wood oil as a gasproof varnish base.

It has been well known in the varnish industry that a whollysatisfactory varnish may not be made up of China-wood oil and eoumaroneresin, the eoumarone resin constituting the entire resin content of thevarnish. This is for the reason that eoumarone resin being neutral, andhaving amongst its advantageous qualities the resistance to dilute acidsand to alkalies attendant upon its neutrality, as a disadvantageousquality forms with China-wood oil a varnish base which when spread as,or incorporated'in, a film gas-checks badly. For this reason it has beennecessary when using eoumarone resin with China-wood oil to add, for thepurpose of avoiding gaschecking, materials wholly different fromeoumarone resin, such as a high acid number resin, of which rosin is thetypical example, or lead compounds and other non-resinous materials. i

- The inclusion of rosin in a substantial proportionresults in a loss ofinertness and neutrality in, a varnish film comprising the vehicle; andmay be considered generally as a deleterious in- 'gredient of a varnish.The gas-checking of a eoumarone and China-wood film is, however, of soserious. a nature that eoumarone resin is not used in association withChina-wood oil in a varnish Vehicle unless there is also included aresin'of high acid number, such 'as rosin, orsome non-resinousinhibitor.

I have discovered that a coumaroneresin, in which the eoumarone ismodified .during .the polymerization process bywhich it is-produced witha phenolic reagent, such as cresol, phenol, xylenol, or the like, inorder to render it alcohol soluble, is additionallycapable of formingwith China-wood oil a varnish base which in a film is not susceptible togas-checking. This discovery is surprising for the reason that theeoumarone resin so modified has still a low acid number. Becauseof thelow acid number of the modified coumarone,.the resin still soapproximates neutrality that a film formed by a varnish, the base ofwhich consists of this .modified eoumarone and China-wood oil, has goodalkali resistance and other good qualities. The phenolic modification ofthe eoumarone resin, however, in spite of the relatively low acid numberimparted by the modification, serves, as above noted, to preventgas-checking in a deposited film containing the modified eoumarone andChina-wood oil.

The phenol-modified eoumarone resin, which possesses this unexpectedconjunction of qualities in association withChina-wood oil, is formedbyincluding and reacting a phenolic substance, such as cresol, phenol,or other phenolic reagent capable of reacting with the polymerizableconstituents of crude solvent naphtha, with crude solvent naphtha andpromoting simultaneously polymerization in the constituents of thenaphtha and reaction of them with the phenolic reagent. Thus a suitablyreactive phenolic substance, such as cresol, phenol, alpha-naphthol, andthe like, may be caused to react with eoumarone, indene,dicyclopentadiene, and the like contained in crude solvent naphtha toproduce as a product of polymerization and phenol reaction a eoumaroneresin formed of polymers of the naphtha-contained constituents reactedwith the phenol.

The procedure involved in producing such a phenol modified eoumaroneresin may be as disclosed in German patent to Ruetgerswerke No. 302,543of 1917, or in accordance with the procedure disclosed in either of myco-pending applications Serial No. 53,514, filed December 9, 1935, orSerial No. 55,613, filed December 21, 1935.

;,-, In accordance with the procedure of my lastnamed applicationserialNo. 55,613, which follows the principles disclosed in German Patent No.302,543, crude solvent naphtha and a phenol are commingled, in suchproportion that the phenol is included in a quantity by weight not lessthan 22% the weight of the polymerizables of the crude solvent naphtha.By means of a small quantity of sulphuric acid, or suitable derivativeof sulphuric acid, both the reaction of polymerization and reactionbetween the polymerizable bodies and the phenol is promoted. During theprogress of reaction, the temperature of the reaction mixture ismaintained below 0., and desirably within the range of 25 C. to 35 C.

,In accordance with the procedure of my copending application Serial No.53,514, a phenolmodified eoumarone resin is produced by comminglingcrude solvent naphtha containing .polymerizable bodies, suchascoumarone, indene, and dicyclopentadiene, with a phenolic substance,such as cresol, phenol, or the like, reactive with them, and by means ofagitation with activated clay in substantial quantity and with use ofmoderately elevated temperature in the neighborhood of C. bothpolymerizing reaction and reaction between the polymerizables and thephenol is promoted.

It may be noted that in general the product of my last-named applicationhas a higher acid number than that of the phenol modified coumaroneresin in which a sulphuric acid base catalyst is utilized to promote thereactions. By

practicing either of these methods, I am able to obtain aphenol-modified resin, which by solvent classification may be sophenol-modified as to have an acid number of 10, or even higher. Forassociation with China-wood oil, however, it .is not necessary that thecoumarone be so phenol modified as to have so high an acid number.

In making a varnish base of the phenol-modified coumarone resin andChina-wood oil, these ingredients may be included in any of the relativeproportions of resin to China-wood oil commonly employed in thepreparation of varnish containing China-Wood oil and resin. Thus themodified coumarone may be used in a short wood oil varnish containing100 pounds of resin 'to gallons of China-wood oil, or in a long wood oilvarnish containing 100 pounds to 50 gallons of China-wood oil, toproduce in both instances a varnish which forms a film proof againstgaschecking. The varnish may be prepared in accordance with the wellknown standard proceedure in making China-wood oil varnishes. Aftercooking in the usual manner, the varnish base is commingled withevaporative solvents, driers, and other varnish ingredients inaccordance with known formulae for China-wood oil varnishes.

In order to prevent the phenomenon of gaschecking, I have found that themodified coumarone need have an acid number no higher than 5, and thatit may in fact have an acid number as low as 2 to 2 without rendering adeposited film of the varnish base susceptible to gas-checking. Thus, ifI utilize a phenol-modified coumarone resin having an acid number of 5,which is the acid number naturally attendant upon the practice of themethod disclosed in my application Serial No. 53,514, thisphenol-modified coumarone may be utilized as no more than half the resincontent of a China-wood oil varnish base, the remaining half of theresin content being a coumarone resin resultant from straightpolymerization.

In connection with the varnish base, I have discovered that the presenceof the phenol-modified coumarone serves greatly to decrease skinningtendencies in the China-wood oil varnish when permitted to stand, whilegiving none the less a quick-drying film.

Any content of phenol-modified coumarone resin in the coumarone contentof a coumarone resin and China-wood oil varnish base tends to lessengas-checking in a varnish film comprising the base. I prefer, however,to use such content of the modified coumarone, modified in such degree,that the acid number of the total content of modified coumarone resin isbetween 2 and 10. If the average acid number of the total coumaronecontent be below 2, I have found that a tendency toward gas-checkingdevelops, and if it be over 10 the hardness and alkali resistance of thevarnish film suffers impairment.

Whereas it has been possible to produce relatively satisfactory filmsfrom a varnish base containing China-Wood oil and one of the more irivolved and expensive synthetic resins, I have discovered that a varnishbase, in which the relatively inexpensive phenol-modified coumaroneresin is incorporated, is at least equally satisfactory in the qualityof being proof against gaschecking, and is more satisfactory than thosebases containing more expensive resins and China-wood oil in the qualityof alkali resistance.

It is to be understood that either phenol-modifie'd coumarone alone, ora mixture of straight coumarone resin and phenol-modified coumaroneresin, may be used in conjunction with other resins in a China-wood oilbase. If the other resin be rosin, or the like resin, its inclusion isdeleterious to the extent that it is included. If it be a resin of themore desirable sort, compatible with the phenol-modified coumarone andnot detrimental to alkali resistance and hardness of the varnish film,the mixture of both with the China-wood oil may be employed withsatisfactory results. The coumarone resin substantially phenol-modifiedis, however, so economical in cost and so satisfactory in associationwith China- Wood oil, that it desirably is made the entire resin contentof a resin and China-wood oil varnish base.

I claim as my invention:

1. A varnish base comprising China-wood oil and alcohol-solublephenol-interacted coumarone resin of low acid number, said resin beingpresent in an amount such as to inhibit gas-checking during drying of avarnish film comprising said base.

2. A varnish base comprising China-wood oil and alcohol-solublecoumarone resin formed by polymerization in the presence of a phenol,said resin having a low acid number and being present in an amount suchas to inhibit gas-checking during drying of a varnish film comprisingsaid base.

3. A varnish base comprising China-wood oil, coumarone resin, andalcohol-soluble phenolinteracted coumarone resin of low acid number, theproportion of said phenol-interacted coumarone resin being such as toinhibit gas-checking during drying of a varnish film comprising saidbase.

4. A varnish base according to claim 1, said resin having an acid numberbetween about 2 and 10.

5. A varnish base according to claim 3, the average acid number of thecoumarone resin content being between 2 and 10.

6. A varnish base comprising a cooked product of China-wood oil andalcohol-soluble phenolinteracted coumarone resin of low acid number,said resin being present in an amount such as to inhibit gas-checkingduring drying of a varnish film comprising said base.

7. A varnish base comprising a cooked product of China-wood oil,coumarone resin, and an alcohol-soluble phenol-interacted coumaroneresin of low acid number, the proportion of said. phenolinteracted resinbeing such as to inhibit gaschecking during drying of a varnish filmcomprising said base.

JOSEPH RIVIHN.

